Steve Bachrach has just blogged on a recent article[1] claiming the isolation of a compound with a C≡S triple bond;
The so-called Fine tuned model of the universe asserts that any small change in several of the dimensionless fundamental physical constants would make the universe radically different (and hence one in which life as we know it could not exist). I suggest here that there may be molecules which epitomize the same principle in chemistry. Consider for example dimethyl formamide. The NMR spectra of this molecule reveal that at room temperature, the two methyl groups are inequivalent, indicating that the rate constant for rotation about the C-N bond has a very particular range of values at the temperatures at which most living organisms exist on our planet.
Curly arrow pushing is one of the essential tools of a mechanistic chemist. Many a published article will speculate about the arrow pushing in a mechanism, although it is becoming increasingly common for these speculations to be backed up by quantitative quantum mechanical and dynamical calculations. These have the potential of exposing the underlying choreography of the electronic dance (the order in which the steps take place). The basic grammar of describing that choreography tends to be the full-headed curly arrow for closed shell systems and its half-barbed equivalent for open shell systems. An effectively unstated and hence implicit rule for closed shell systems is that only one curly arrow is used per breaking or forming bond, i.e. electrons move around bonds in pairs. So consider the following reaction (inspired by a posting on Steve Bachrach’s blog)
In an earlier post I wrote about the iconic SN1 solvolysis reaction, and presented a model for the transition state involving 13 water molecules. Here, I follow this up with an improved molecule containing 16 water molecules, and how the barrier for this model compares with experiment. This latter is nicely summarized in the following article: Solvolysis of t-butyl chloride in water-rich methanol + water mixtures, which (for pure water) cites the following activation parameters
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We have seen in the series of posts on the topic of hypervalency how the first row main group elements such as Be, B, C and N can sustain apparent hypercoordination and arguably hypervalency. The latter is defined not so much by expanding the total valence shell of electrons surrounding the hypervalent atom beyond eight, but in having more than four well defined bonds to it, as quantified by AIM and ELF analysis. The previous post made the suggestion of how a compound involving hypervalent boron could also sustain a genuine bond to the rare gas helium. It is surely time to seek evidence that this type of bonding can be sustained in reality. Fortunately, a crystal structure of a reasonably analogous compound IS available (DOI: 10.1016/0022-328X(94)05089-T).
Quite a few threads have developed in this series of posts, and following each leads in rather different directions. In this previous post the comment was made that coordinating a carbon dication to the face of a cyclopentadienyl anion resulted in a monocation which had a remarkably high proton affinity. So it is a simple progression to ask whether these systems may in turn harbour a large affinity for binding not so much a H+ as the next homologue He2+?
The previous posts have seen how a molecule containing a hypervalent carbon atom can be designed by making a series of logical chemical connections. Another logical step is to investigate whether the adjacent atoms in the periodic table may exhibit similar effects (C2+ ≡ B+ ≡ N3+ ≡ Be ≡ O4+). So here are reported some results (B3LYP/6-311G(d,p) ) for boron, beryllium and nitrogen, for the general tetramethyl substituted system shown below
The previous post talked about making links or connections. And part of the purpose for presenting this chemistry as a blog is to expose how these connections are made, or or less as it happens in real time (and not the chronologically sanitized version of discovery that most research papers are). So each post represents an evolution or mutation from the previous one. To recapitulate, we have seen how the idea of cyclopentadienyl anion as a ligand for a dipositive carbon atom has evolved. Let us move in yet another direction; the cyclobutadienyl dianion. This ligand has recently been shown to bind Mg2+ (DOI: 10.1002/ejic.200800066), so why not He2+? And picking up again the previous theme, we will then protonate the bound complex. The result now is a monocation, and it has the C4v-symmetric structure shown below (DOI: 10042/to-2438). This bears some resemblance to pyramidane, a neutral C5H4 compound with hemispherical carbon reported in 2001[1] which is also a stable minimum in the potential energy surface.
Science is about making connections. And these can often be made between the most unlikely concepts. Thus in the posts I have made about pentavalent carbon, one can identify a series of conceptual connections. The first, by Matthias Bickelhaupt and co, resulted in the suggestion of a possible frozen SN2 transition state. They used astatine, and this enabled a connection to be made between another good nucleophile/nucleofuge, cyclopentadienyl anion. This too seems to lead to a frozen Sn2 transition state. The cyclopentadienyl theme then asks whether this anion can coordinate a much simpler unit, a C2+ dication (rather than Bickelhaupt’s suggestion of a (NC)3C+ cation/radical) and indeed that complex is also frozen, again with 5-coordinate carbon, and this time with five equal C-C bonds. So here, the perhaps inevitable progression of ideas moves on to examining the properties of this complex, the outcome being a quite counter-intuitive suggestion which moves us into new territory.